Manufacture of aromatic arylsulphonyl and arylene-disulphonyl derivatives of 1:4 naphthylenediamine and its sulphonic acids



ilpplieatioii filed June 29,

pnznic acids of these compounds.

,Ui? these groups of compounds, only one, 1 3k; snel y henzenesniphonyl-1 l-naphthyleneline, has hitherto been described, havsen o"hie-sly prepared by roundabout suits-lilo for employment under conditions (Morgan end Mick- Trens. 1905. 87. 929). "ion is based upon the observa- I. i oi'lifg ot the groups of e' tinned mef jce prepared by a gen.- 1 s,

producing such bodies eethe inventionjcoinprises reducing o crpcro nitroderivetives of the vi ca nephth rijeinines or arylene enyl his cz nophthyleinines or their onic ocifs containing the sulphonic lid" t e positions 2, 6, 7 or 8 with r' 1 I oir lsulphonylmnino or nrylene own phonyleinino radical the emplovment t reducing medium which is neit or so ",r acid nor so stronglynlkeline that iytic change and elimination of a-rylhonyl or erylene disulphonyi groups during the operation.

e invention more prticularly consists he process of producing ervlsulphonyl n ohthyleno(lion hnes ArQ-SO NHIC no disulphon rl-his-l l-naphsi ir" (SO .Nl'l.C 'il,.Nll,) ic acids of these compounds forming pare ezo deriven'r yl sulphonyl nophthyl UELIAS MORGAH, {1F LONDUN, EEGLED, AS$IGNOB T0 Il El-E'EBIAL TRUST ENT'QF SCKEN'EIFIC AND IIIIDUSTEIAJL :R-ESMXRCH, 9F WEST- 033' ARQBIATEG ABYLSUISLPHOIQ'YL AND AEYLENE-DISULPHQNYE fi 01; 1:4 IIAPHTHYLENEDIEIEINE AND E' ETLFLEIQIEH'! AGREE-2.

1920. serial No. 3992,731

amines or orylene disulphonyl his a nophthylninines or their snlphonie acids containing the snlphonic radical in the positions 2, 6, '4' or 8, with respect to the eryl sulphonylamino or erylene disulphonyl amino radical to react with diezonium compounds as, for instance, benzene diazonium chloride, ortho and para'toluene diazonium chlorides, a and 6' nephthelenediczoniuinchlorides and the like in alkaline media, and efiecting the reduction of the pare-e derivatives thus produccd in the manner specified above.

The invention also consists in condensing 0: naphthylamine or or naphthylemine sulphonic acids containin the following groups in the relative posltions indicetecl:--

Nfi zl; 50 E119, 6, 7 or 8 with a-rylenedisiilpho nic acid chlorides Ar"(S0,G1) de;

rived, for instance, from benzene, toluene or their homologues or from naphthalene, causing the cryl'enedisulphonylbis 0: naphthylamine or the solphonic acids thereof thereby formed to reset with dialzonium compounds and reducing the pore! azo derivetives thus produced in the manner s'pecified above.

The conddnsctiofi o f tle c2 nenhth'ylemine or e nephthjvleinin' sulp onic'. acids with an arylene iziisnl'phonic chloride may conveniently he efi'ec'ted by fixing c hophthylaznine or the alkalisalt of'orie of its siilphonic acids as specified above, with a n erylene disulphonic chloride ifrthe presence of pyridine,

anhydrous sodium acetlite or some other reagent caiaable'offfixing the hydrogen chloride set free during reaction.

'Ehe redirctionof the para no derivatives may he coihnletely effected Without hydroly sis 0r elimination (attire orylsulphonyl or ierylenedisulphonvl groups giving rise to a 'rylsnlphonyl and erylenedisnlgohonyi derivatlrves'of 1:42 naphthylenediornine or its sulphonic acids containing the snlphonic radical in positions 2, 6, 7 or 8 with respect to the ai vlsulphonylamino-rsdicel. This re duction can he carried out with commercially available reagents such es zine and aqueous caustic soda, zine dust ammonium chloride, iron borings and dilute acids, ellmlinc sodium hydrosulphite, oilinline sodium sulohide, ste-nnous chloride or timezone chloride, providing that the medium acetic acid mas O HHg tion of the pare-212:0 derivatives; plionyl-czmaphi i *1 of aryleul "HiallXES and ar y'leiiieui phonyl-bis-wnn llliylamiiies may be r seilted by the fol owing foimii 1'. F-rorluciimi of (an erg L9wiphongzid -n a 10 MM le'rwomiiiio phonic radicals, who laicourse,

F or the purpose of illinitiation certain examples of suitable ways in which the in vention may be armed into effect are iVQIZ below in ,WhlCl'L 1 imples, the propor m of l l l.

materials med are sis ed. 111 p:

Ten aris oi amina-: 15

toluene-p-solplxonie nlilo ide and. 11.5 purl-:1,

of anhydrous sodium gether until the p; The toluenop s .lohonyl-a-x. liylmnine is Waghed with aqueous sodiu "lionate to remove unaltered i011?8D-P-Sill l10fil0 chloride and ii par-ts are dissolved in 13 parts of 5 normal sodium hydroxide end 30 parts of wateg and treats-:1 in the cold with benzene dia'zonium chloride oht 218d fYOIll 1.9 parts of aniline. The sodium Stilt of heme/flea:- azotoluene p anlplionyl-ornaplwhy iiuine separates as a sparingly soluble viscid mass soluble in alcohol from which solution dilute precipitates the free azo-oum pound. melting; at 203 ("Will gives 201 Berichte. 2? 2372).

Eight parts of bemzeiiel-m-zo-p--toluenesul phonyLce-naplithylamilie is: dissolved in 30 parts of alcohol anol 30 parts of water eon tainingOB parts of ammonium chloride in vessel fitted with an efiicien fi s 'x' rer. To the boiling solutioii parts of zinc cliisc are slowly added, i: heating continued until.

'zecl when the liquid iiw'mies solid,

e ground to pinkish wlziitte precipitate wliiqli when or 1531-1-98. v

' Emu/"agile ?2.----Fmw parts of the QZO-CQD1- pound of the prec ing example are dis solved in 1000 parts of ater containing 25 part-s 3f 'i'ioioizil r-iodiuii'i liy'roXide. solution is heated ho 50-60 L 530% solution of sodium liyrlrosulphite are slowly added with continual imitil the solution is tlecolourized. The filtered so lui" 3'21 is then acidified with dilute oce'lie or 2nd rocliloziie acid and ilze procloct is iselaie l' in example stal izedmeita at iner and line pasty mass ween 1e and after stirring for about 2 hours the liquid is acidified with. dilute mineral acid or acetic acid. The azo-compound sepa-' rates in ochre yellow masses.

Four parts of the azo-compound are dis solved in parts of 5 normal sodium hydroxide and ZOO-parts of water, the solution heated to 100 and l parts of zinc dust slowly added and the heating continneduntil Two parts of e-naphthyiamine, 2.5 parts of naphthalene-2 2 G-disulphonic chloride (in. p.226?) and three parts of anhydrous sodium acetate are mixed together, slightly warmed and the mixture treated with aqueous sodi- "um carbonate and the product isolated as in Example 3'. Five parts of naphthalene-2 41. disulphonyl hise-naphthylamine dissolved in parts of 5 normal sodium hydroxide and 200 parts of water are treated with hen zenedlazoniuln chloride derived from 1.8

parts of aniline. The solution isniaintained alkaline, throughout the coupling and the dark brownish red azo-compound, C ltl tated by the addition of dilute acid.

Seven parts ofthis azo-compound are dis solved in 4:0 partsof 5 normal sodium hydroxide and 200 parts of water and reduoed at 100 with 12 parts of zinc dust. The de-. eolourized solution is filtered and acidified when the naphthalene-2: G-disulphonyl-biS- 1: l-naphthylenediamine is precipitated.

Emample 5.1 toZuem-p-sulpiwnyZ-J v maphthyleaed'emhvw-8--sulpfwnic. acid:

Five parts of a-naphthylamine-Elsuphonie acid, L3 parts of toluene-p-sulphonic chlo ride, 3 parts of anhydrous sodium acetate and one part of pyridine are ;warrned to gether and the pasty muss isilissolved in warm aqueous sodium carbonate. The cold filter d solution istreated with henzenedia- I zoniuin chloride from 1:8 parts of aniline.

The solution of azo-compound isreduced with QO'parts of zinc dust and parts of 5 normal sodium hydroxide and the cold de-- colourized filtratetreated with dilute acetic acid when the product is obtain :1 as a yel-. lowishwhite precipitate becoming light purple on exposure to light and air.

' The other sulphonie acids of the arylsulphonyl-a;haphthylarninesare produced in a similar mannenhy replacing the oz-naphthe solution'is decolouriz-ed. After filtering from the zinc dust and oxide the solution is acidified and the henzene l:3-disulphonylhis-1:l-naphthylene-diarnine is isolated in themanner described in the preceding e1;- amples. v

nyZ-bis-l il-naphzihg knedemna thylanaine-dsulphonic acid in this example by oi-naphthylamine-7-sulpl1onic acid or o:- naphthylamine-fiisulphonic acid or e-naphthylaznine-2-sulphonic acid.

Four parts 01"" e-naphthylaminefisulphonic acid (Scholkopf acid), 3-2 parts of benzene-l :8-di'sulphonic. chlorid'e'and 2 parts of sodium acetate are ground together and the mass moistened Withone part of pyridine warmed gently till the mixture is complete. Acetic acid 18 evolved and the pasty mass stifi ens. Any unchanged henzene-1:3-.

disulphonio chloride is decomposed with sodium earhonate and the intermediate pro driot-is obtained partly undissolved and the reniaigider isolated on concentrating the solutidul v Four parts of the bisdisulphonyl' compound are dissolved in 12' parts of 5 normal sodiuzn hydroxide and 200 arts or" water and coupled in alkaline solution with the Example 6.1-henzeqie-B-disulphonyZ-bis- I diamines and the arylene disulphonyl-bis- 1 :+l-naphthylenediamines and their sulplion 1c acids having the sulphonic radical in the position (3, T, (r 8 with respect to the I l. (aryl derivatives), 2. (arylene derivatives), are characterized by the presence 05 a very reactive hydrogen atom in the positions marked by an asterisk in the gen eral forn'iula: and are accordingly of considerable utility in the'production oi orthoazo dyes and of colour producing intermediates.

Claims:

1. The process of producing derivatives of 1:4: naphthylene diamineshaving a hydrogen of an amino group attached to a naphthalene nucleus replaced by an aromatic sulphonyl group, which comprises reducing hy the employment of a weak reducing-medium a para-axe derivative o'l an a naphthylamine derivative having a hydrogen of an amino group attached to a. naphthalene nucleus replaced by an aromatic sulphonyl group.

2. The process of producing; derivatives of 1: naphthylene diamines having a hydrogen oi an amino group attached to a naphthalene nucleus replaced by an aromatic sulphonyl group, which comprises reducing, by the employment of a reducing medium which is neither so strongly acid nor so strongly alkaline that hydrolvtic change and elimination of the aromatic sulphonyl group takes place during the operation, a para-azo derivative of an 0! naphthylamine derivative having a hydrogen of an amino group attached to a naphthalene nucleus replaced by an aromatic sulphonyl group.

so strongly alkaline that hydrolytic change emme e The process of producing derivatives of .l:-l naphthylenediamines containing two a naphthylamine groups and having a hydrogen oi an amino group of each of the naphthylamine groups replaced by a sulphonyl group, which comprises reducin by the employment of a weak reducing medium, a para-axe derivative an 0: naphthylamine derivative containing two a naphtlrvlamine groups, a hydrogen of an amino group of each of which groups is replaced by a. sulphonyl group connected to an arylone group common to the sulphonyl groups.

5 The process of producing derivatives ol 1 lnaphthylene diamines containing two a naphthylamine groups and. having a hydrogen of an amino group of each of the naphthylamine groups replaced by a sulphonyl group which comprises reducing, by the employment of a reducing medium which. is neither so strongly acid nor and elimination of the aromatic'sulphonyl group takes place during the operation, a para-am derivative of an a naphthylamine derivative containing two a naphthylamine groups, a hydrogen oi an amino group of each of which groups is replaced by a sulphonyl group connected to an arylene group common to the sulphonyl groups.

In testimony whereof I have signed my name to this specification.

GILBERT THOMAS MORGAN. 

